CN111471179B - Preparation method of modified fluorosilicone polymer, fabric and application thereof - Google Patents
Preparation method of modified fluorosilicone polymer, fabric and application thereof Download PDFInfo
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- CN111471179B CN111471179B CN202010472216.3A CN202010472216A CN111471179B CN 111471179 B CN111471179 B CN 111471179B CN 202010472216 A CN202010472216 A CN 202010472216A CN 111471179 B CN111471179 B CN 111471179B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000004744 fabric Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 45
- -1 chloropropyl Chemical group 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000004945 silicone rubber Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 8
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- ZLCUIOWQYBYEBG-UHFFFAOYSA-N 1-Amino-2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=C(N)C(C)=CC=C3C(=O)C2=C1 ZLCUIOWQYBYEBG-UHFFFAOYSA-N 0.000 claims description 3
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims description 3
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 claims description 3
- MSSQDESMUMSQEN-UHFFFAOYSA-N 1-amino-2-bromo-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC(Br)=C2N MSSQDESMUMSQEN-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical class [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000987 azo dye Substances 0.000 abstract description 13
- 150000002823 nitrates Chemical class 0.000 abstract description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006065 biodegradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 150000004056 anthraquinones Chemical class 0.000 abstract description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 229920002545 silicone oil Polymers 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 239000011032 tourmaline Substances 0.000 description 3
- 229940070527 tourmaline Drugs 0.000 description 3
- 229910052613 tourmaline Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241001147693 Staphylococcus sp. Species 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003698 anagen phase Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a modified fluorosilicone polymer, a fabric and application thereof, wherein the modified fluorosilicone polymer is obtained by carrying out dehydrochlorination reaction on a fluorosilicone polymer containing chloropropyl and vinyl and an anthraquinone compound containing amino under the action of an acid-binding agent; and the incompatibility of the modified fluorine-silicon polymer and the silicon rubber is utilized to be separated out from the surface for enrichment, so that the anthraquinone with higher content on the surface is obtained, and therefore, the fabric has a better promotion effect on the biodegradation of azo dyes and nitrates.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a preparation method of a modified fluorosilicone polymer, a fabric and application thereof.
Background
The environmental pollution caused by the use of a large amount of azo dyes, nitrates and the like has attracted great attention, anaerobic microorganisms have good application prospects in the degradation of the azo dyes, the nitrates and the like, and redox mediators such as anthraquinone compounds and the like can improve the degradation rate of the anthraquinone compounds by more than 1 order of magnitude. However, in order to avoid "secondary pollution" to water caused by directly using anthraquinone compounds, it has been reported that the anthraquinone compounds are grafted on the surface of carriers such as polymer films (publication No. CN103936146B), fillers (publication No. CN110066009A) and the like through chemical reaction, so as to avoid entering water and be recycled. But is limited by the density of the reaction group on the carrier, the grafting reaction efficiency and other factors, the grafting efficiency is not high, the biodegradation rate of azo dyes, nitrates and the like cannot be improved to meet the expectations of people, and the recycling is inconvenient.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a modified fluorosilicone polymer.
It is another object of the present invention to provide a fabric.
It is also an object of the invention to provide a use of the fabric.
The technical scheme of the invention is as follows:
a preparation method of a modified fluorosilicone polymer comprises the steps of adding 10 parts by weight of fluorosilicone polymer containing chloropropyl and vinyl into 50-200 parts by weight of an organic solvent, dropwise adding a mixed solution consisting of 0.5-3 parts by weight of an amino anthraquinone compound, 0.1-1 part by weight of an acid binding agent and 10-20 parts by weight of the organic solvent at room temperature, stirring and reacting for 1-10 hours, filtering, and removing the organic solvent to obtain the modified fluorosilicone polymer.
Preferably, the general formula of the fluorine-silicon polymer is R1SiMe2O(SiOMeRf)a(SiOMeVi)b(SiOMe2)c(SiOMeRv)dSiMe2R1Wherein R is1Is methyl, vinyl or hydroxy, Me is methyl, RfIs 3,3, 3-trifluoropropyl, Vi is vinyl, RvIs 3-chloropropyl, a is more than or equal to 5 and less than or equal to 20, b is more than or equal to 2.1 and less than or equal to 5, c is more than or equal to 3 and less than or equal to 50, and d is more than or equal to 3 and less than or equal to 7.
Preferably, the amino anthraquinone-containing compound is one or more selected from 2-amino anthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone and 1-amino-2-methylanthraquinone.
Preferably, the acid-binding agent is one or more selected from triethylamine, triethanolamine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and N-methyldiethylamine. More preferably, the acid scavenger is selected from triethylamine, sodium carbonate or N-methyldiethylamine.
A modified fluorosilicone polymer prepared by the preparation method of any one of the above embodiments.
A fabric is processed by silicon rubber and the modified fluorosilicone polymer described in the above embodiments. The processing can be directly processing the silicon rubber and the modified fluorine-silicon polymer into the fabric after being uniformly mixed, such as an injection molding method or an extrusion molding method, or processing the silicon rubber and the modified fluorine-silicon polymer into the fiber after being uniformly mixed, and then spinning the fiber into the fabric or blending the fiber with other fibers into the fabric.
Preferably, the silicone rubber comprises a silicone rubber base and a vulcanizing agent. The vulcanizing agent can be selected from a peroxide vulcanizing agent, a composition of hydrogen-containing silicone oil and a hydrosilylation catalyst or a composition of mercapto silicone oil and a photoinitiator according to different vulcanization modes.
Peroxide curing agents are initiators for crosslinking with peroxides. The peroxide may be selected from 2, 4-dichlorobenzoyl (bis-2, 4), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (bis-2, 5), Benzoyl Peroxide (BPO), dicumyl peroxide (DCP) or Azobisisobutyronitrile (AIBN).
The composition of hydrogen-containing silicone oil and hydrosilylation catalyst takes the hydrogen-containing silicone oil as a cross-linking agent, and the catalyst plays a role of catalysis to promote vulcanization crosslinking. The viscosity (25 ℃) of the hydrogen-containing silicone oil is 30-5000 mPa & s, and the weight percentage of hydrogen is 0.08-0.5%. The catalyst is Karstedt catalyst or speier catalyst.
The composition of the mercapto silicone oil and the photoinitiator takes the mercapto silicone oil as a cross-linking agent, and the photoinitiator plays a role in promoting vulcanization crosslinking. The viscosity (25 ℃) of the mercapto silicone oil is 50-6000 mPa · s, and the weight percentage of mercapto is 0.5-8%. The photoinitiator is preferably a benzoin type initiator, and can be selected from one of benzoin dimethyl ether, benzoin butyl ether or benzoin ethyl ether.
More preferably, the silicone rubber-based rubber is composed of methyl vinyl silicone raw rubber and a filler according to a weight ratio of 1: 0-4. The filler can be selected from at least one of fumed silica, precipitated silica, graphene, alumina, aluminum hydroxide, glass fiber, glass microsphere, tourmaline and calcium carbonate.
Preferably, the weight ratio of the silicone rubber to the modified fluorosilicone polymer is 100: 0.05-2.5. More preferably, the weight ratio is 100: 0.1-1.5.
Use of a fabric according to any one of the preceding embodiments in the field of wastewater treatment. Preferably, the application in wastewater containing azo dyes and nitrates.
The fluorine-silicon polymer is incompatible with the silicon rubber, so that the modified fluorine-silicon polymer after anthraquinone is grafted on the side chain of the fluorine-silicon polymer can migrate to the surface of the silicon rubber and is fixed on the surface of the silicon rubber through curing and reaction of the silicon rubber, and therefore, the fabric obtained by mixing and processing the modified fluorine-silicon polymer and the silicon rubber has a better promotion effect on biodegradation of azo dyes and nitrates.
The invention has the beneficial effects that:
(1) the fabric has a good biodegradation promoting effect on azo dyes and nitrates, and can be applied to biodegradation of azo dyes and nitrates;
(2) the shape and the structure of the fabric can be woven according to requirements, the fabric is convenient and flexible, the recoverability is good, and in an application method, the fabric can be woven into a structure similar to a fishing net, so that the use convenience is improved; meanwhile, the modified fluorosilicone polymer containing anthraquinone is chemically fixed on the surface of the fabric, so that the stability is good, and the fabric can be repeatedly used.
(3) The method is simple and low in cost.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Examples 1 to 4 are for preparing modified fluorosilicone polymers, in which,
the general formula of the fluorine-silicon polymer A containing chloropropyl and vinyl is SiMe3O(SiOMeRf)14.6(SiOMeVi)2.7(SiOMe2)22.1(SiOMeRv)3.8SiMe3，Me、Rf、Vi、RvAs described above;
the general formula of the fluorine-silicon polymer B containing chloropropyl and vinyl is ViSiMe2O(SiOMeRf)9.5(SiOMeVi)4.2(SiOMe2)15.7(SiOMeRv)6.3SiMe2Vi，Me、Rf、Vi、RvAs described above;
the general formula of the fluorine-silicon polymer C containing chloropropyl and vinyl is HOSiMe2O(SiOMeRf)8.2(SiOMeVi)3.9(SiOMe2)35.3(SiOMeRv)4.2SiMe2OH，Me、Rf、Vi、RvAs described above;
example 1
Adding 10 parts by weight of fluorine-silicon polymer A containing chloropropyl and vinyl into 80 parts by weight of tetrahydrofuran, dropwise adding a mixed solution consisting of 0.5 part by weight of 2-aminoanthraquinone, 0.15 part by weight of triethylamine and 10 parts by weight of tetrahydrofuran at room temperature, stirring and reacting for 7 hours, filtering, and filtering out liquid to remove tetrahydrofuran and unreacted triethylamine to obtain the modified fluorine-silicon polymer, which is marked as S-1.
Example 2
Adding 10 parts by weight of fluorine-silicon polymer B containing chloropropyl and vinyl into 150 parts by weight of butyl acetate, dropwise adding a mixed solution consisting of 1.8 parts by weight of 1-aminoanthraquinone, 0.6 part by weight of sodium carbonate and 15 parts by weight of butyl acetate at room temperature, stirring for reaction for 9 hours, filtering, and filtering out liquid to remove butyl acetate to obtain a modified fluorine-silicon polymer, which is marked as S-2.
Example 3
Adding 10 parts by weight of fluorine-silicon polymer C containing chloropropyl and vinyl into 200 parts by weight of butanone, dropwise adding a mixed solution consisting of 3 parts by weight of 1-amino-2-methylanthraquinone, 1 part by weight of sodium hydroxide and 20 parts by weight of butanone at room temperature, stirring for reacting for 3 hours, filtering, and filtering out liquid to remove the butanone to obtain the modified fluorine-silicon polymer, which is marked as S-3.
Example 4
Adding 10 parts by weight of fluorine-silicon polymer B containing chloropropyl and vinyl into 130 parts by weight of tetrahydrofuran, dropwise adding a mixed solution consisting of 1.5 parts by weight of 2-aminoanthraquinone, 0.5 part by weight of sodium hydroxide and 14 parts by weight of tetrahydrofuran at room temperature, stirring for reacting for 2.5 hours, filtering, and filtering out liquid to remove tetrahydrofuran to obtain a modified fluorine-silicon polymer, which is marked as S-4.
Examples 5-10 are for the preparation of fabrics
Example 5
The methyl vinyl silicon crude rubber, the fumed silica and the tourmaline are mixed and processed into the silicon rubber base rubber according to the weight ratio of 1:0.25: 0.2.
The silicone rubber base rubber and the bis-2, 4 are mixed and processed into the silicone rubber according to the weight ratio of 100: 1.5.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-1 according to the weight ratio of 100:0.12, extruding, and vulcanizing at 120 ℃ for 12 minutes to obtain fibers; the fibers were woven into a fabric, designated F-1.
Example 6
The methyl vinyl silicon crude rubber and the alumina are mixed and processed into the silicon rubber base rubber according to the weight ratio of 1: 0.6.
The silicone rubber base gum and the hydrogen-containing silicone oil (containing 90ppm Karstedt catalyst) are mixed according to the weight ratio of 100:6 and processed into the silicone rubber.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-2 according to the weight ratio of 100:0.6, extruding, and vulcanizing at 140 ℃ for 10 minutes to obtain fibers; the fibers were woven into a fabric, designated F-2.
Example 7
The methyl vinyl silicone crude rubber and the precipitated silica white are mixed and processed into silicone rubber base rubber according to the weight ratio of 1: 0.33.
The silicone rubber base rubber and the mercapto silicone oil (containing 10 weight percent of benzoin butyl ether) are mixed and processed into the silicone rubber according to the weight ratio of 100: 5.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-3 according to the weight ratio of 100:1.2, extruding, and obtaining the product with the light intensity of 10mW/cm2Irradiating and vulcanizing for 90s by using ultraviolet light to obtain fibers; the fibers were woven into a fabric, designated F-3.
Example 8
The methyl vinyl silicon rubber, the fumed silica and the tourmaline are mixed and processed into the silicon rubber base rubber according to the weight ratio of 1:025: 0.2.
The silicone rubber base rubber and the bis-2, 4 are mixed and processed into the silicone rubber according to the weight ratio of 100: 1.5.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-4 according to the weight ratio of 100:2.3, extruding, and vulcanizing at 120 ℃ for 12 minutes to obtain fibers; the fibers were woven into a fabric, designated F-4.
Example 9
The methyl vinyl silicone crude rubber and the fumed silica are mixed and processed into silicone rubber base rubber according to the weight ratio of 1: 0.35.
The silicone rubber base gum and the hydrogen-containing silicone oil (containing 90ppm Karstedt catalyst) are mixed according to the weight ratio of 100:8 and processed into the silicone rubber.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-2 according to the weight ratio of 100:1.6, extruding, and vulcanizing at 150 ℃ for 10 minutes to obtain fibers; the fibers were woven into a fabric, designated F-5.
Example 10
The methyl vinyl silicone rubber and the hydrogen-containing silicone oil (containing 90ppm Karstedt catalyst) are mixed and processed into the silicone rubber according to the weight ratio of 100: 10.
Mixing and processing the silicon rubber and the modified fluorine-silicon polymer S-1 according to the weight ratio of 100:1.8, extruding, and obtaining the product with the light intensity of 10mW/cm2Irradiating and vulcanizing for 50s by using ultraviolet light to obtain fibers; the fibers were woven into a fabric, designated F-6.
Comparative example 1
Anthraquinone-modified talc, denoted C-1, was prepared according to the method of example 3 in patent application publication No. CN 110040844A.
Comparative example 2
An anthraquinone-modified nylon membrane, designated C-2, was prepared according to the method of example 1 in the patent granted under publication No. CN 103936146B.
Comparative example 3
The silicone rubber, 2-aminoanthraquinone, and fluorosilicone polymer B containing chloropropyl and vinyl in example 7 were compounded at a weight ratio of 100:0.4:1, extruded, and vulcanized for 90 seconds under ultraviolet irradiation at a light intensity of 10mW/cm to obtain fibers; the fibers were woven into a fabric, designated C-3.
Comparative example 4
The silicon rubber and the 2-aminoanthraquinone in the embodiment 7 are mixed and processed according to the weight ratio of 100:0.5, extruded and vulcanized for 90s under the irradiation of ultraviolet light with the light intensity of 10mW/cm to obtain fibers; the fibers were woven into a fabric, designated C-4.
The effect on the acceleration of the degradation of azo dyes was tested: after 2g of a sample to be tested is respectively washed by physiological saline for 3 times, the sample is added into 200ml of 120mg/L acid red B containing azo dye degradation strain GYZ (staphylococcus sp.) in logarithmic growth phase for decolorization test, and the change of the concentration of the acid red B along with time is determined. The results are shown in Table 1.
TABLE 1 acid Red B concentration/mg/L
| 0h | 2h | 4h | 6h | 8h | |
| F-1 | 120 | 99 | 71 | 26 | 3 |
| F-2 | 120 | 95 | 63 | 21 | 2 |
| F-3 | 120 | 94 | 61 | 18 | ＜1 |
| F-4 | 120 | 93 | 59 | 16 | ＜1 |
| F-5 | 120 | 95 | 62 | 17 | 1 |
| F-6 | 120 | 93 | 60 | 17 | 2 |
| C-1 | 120 | 104 | 82 | 48 | 13 |
| C-2 | 120 | 100 | 75 | 42 | 6 |
| C-3 | 120 | 108 | 95 | 77 | 51 |
| C-4 | 120 | 104 | 92 | 73 | 48 |
The test has an accelerating effect on the nitrate degradation: after 2g of samples to be tested are respectively washed by physiological saline for 3 times, the samples are added into 200ml of nitrate wastewater containing denitrifying microorganisms in logarithmic growth phase and 150mg/L for testing, and the change of the nitrate concentration along with time is measured. The results are shown in Table 2.
TABLE 2 nitrate concentration/mg/L
| 0h | 2h | 4h | 6h | 8h | |
| F-1 | 150 | 115 | 82 | 49 | 18 |
| F-2 | 150 | 109 | 75 | 42 | 11 |
| F-3 | 150 | 110 | 77 | 41 | 12 |
| F-4 | 150 | 109 | 76 | 38 | 12 |
| F-5 | 150 | 112 | 74 | 40 | 13 |
| F-6 | 150 | 111 | 74 | 40 | 13 |
| C-1 | 150 | 122 | 94 | 65 | 27 |
| C-2 | 150 | 120 | 92 | 67 | 28 |
| C-3 | 150 | 133 | 110 | 91 | 70 |
| C-4 | 150 | 130 | 104 | 85 | 68 |
Repeated use test: after 2g of a sample to be tested was washed with physiological saline for 3 times, the sample was added to 200ml of 120mg/L acid red B containing an azo dye degradation strain GYZ (staphylococcus sp.) in the logarithmic phase to perform a decolorization test, and the concentration of acid red B after 6 hours was measured. And cleaning and drying the tested sample by using clean water, performing decolorization test for 6 hours by using acid red B according to the method, and repeatedly testing for 12 times. The results are shown in Table 3.
TABLE 3 acid Red B concentration/mg/L
| Number of tests | F-1 | F-2 | F-3 | F-4 | F-5 | F-6 |
| 1 st time | 26 | 21 | 18 | 16 | 17 | 17 |
| 2 nd time | 26 | 21 | 15 | 15 | 19 | 18 |
| 3 rd time | 28 | 20 | 19 | 16 | 20 | 16 |
| 4 th time | 24 | 17 | 18 | 15 | 16 | 16 |
| 5 th time | 25 | 19 | 18 | 17 | 18 | 16 |
| 6 th time | 26 | 21 | 16 | 18 | 17 | 18 |
| 7 th time | 28 | 18 | 16 | 17 | 19 | 19 |
| 8 th time | 25 | 20 | 19 | 19 | 18 | 17 |
| 9 th time | 27 | 18 | 17 | 16 | 20 | 17 |
| 10 th time | 25 | 19 | 20 | 17 | 17 | 19 |
| 11 th time | 26 | 21 | 17 | 17 | 18 | 19 |
| 12 th time | 27 | 19 | 19 | 18 | 18 | 19 |
Therefore, the fabric obtained by preparing the modified fluorosilicone polymer and adding the modified fluorosilicone polymer into the silicone rubber composition can obviously improve the biodegradation rate of the acid red B and the nitrate, is more convenient to recover compared with filler particles and polymeric films in a particle form, and can be repeatedly used.
Therefore, the fabric can be applied to the treatment of wastewater containing azo dyes, nitrates and the like, and can obviously improve the biodegradation rate of the azo dyes and the nitrates.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a modified fluorosilicone polymer is characterized by adding 10 parts by weight of a fluorosilicone polymer containing chloropropyl and vinyl into 50-200 parts by weight of an organic solvent, dropwise adding a mixed solution consisting of 0.5-3 parts by weight of an amino anthraquinone compound, 0.1-1 part by weight of an acid-binding agent and 10-20 parts by weight of the organic solvent at room temperature, stirring and reacting for 1-10 hours, filtering, and filtering out liquid to remove the organic solvent to obtain the modified fluorosilicone polymer;
the general formula of the fluorine-silicon polymer is R1SiMe2O(SiOMeRf)a(SiOMeVi)b(SiOMe2)c(SiOMeRv)dSiMe2R1Wherein R is1Is methyl, vinyl or hydroxy, Me is methyl, RfIs 3,3, 3-trifluoropropyl, Vi is vinyl, RvIs 3-chloropropyl, a is more than or equal to 5 and less than or equal to 20, b is more than or equal to 2.1 and less than or equal to 5, c is more than or equal to 3 and less than or equal to 50, and d is more than or equal to 3 and less than or equal to 7.
2. The production method according to claim 1, wherein the aminoanthraquinone-containing compound is one or more selected from the group consisting of 2-aminoanthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone and 1-amino-2-methylanthraquinone.
3. The preparation method of claim 1, wherein the acid-binding agent is selected from one or more of triethylamine, triethanolamine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and N-methyldiethylamine.
4. A modified fluorosilicone polymer, characterized by being prepared by the preparation method according to any one of claims 1 to 3.
5. A fabric obtained by processing a silicone rubber and the modified fluorosilicone polymer according to claim 4.
6. The fabric of claim 5, the silicone rubber comprising a silicone rubber base and a vulcanizing agent.
7. The fabric according to claim 6, wherein the silicone rubber-based rubber comprises methyl vinyl silicone gum and a filler in a weight ratio of 1: 0-4.
8. The fabric according to claim 5, wherein the weight ratio of the silicone rubber to the modified fluorosilicone polymer is 100: 0.05-2.
9. Use of a fabric according to any one of claims 5 to 8 in the field of wastewater treatment.
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